Model-Based Identification and Experimental Validation of the Optimal Reaction Route for the Hydroformylation of 1-Dodecene

Hentschel, Benjamin; Kiedorf, Gregor; Gerlach, Martin; Hamel, Christof; Seidel‐Morgenstern, Andreas; Freund, Hannsjörg; Sundmacher, Kai

doi:10.1021/ie504388t

Cited by 51 publications

(66 citation statements)

References 21 publications

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“…This benchmark of thermochemical data of long chain olefins will help to assign parameters required in the kinetic network model for the hydroformylation process. 63,64 The steric demand by the biphenylbisoxy ligand parts poses a steric restriction to coordination of internal n-decene isomers.…”

Section: Discussionmentioning

confidence: 99%

The thermochemistry of long chain olefin isomers during hydroformylation

Kohls

Stein

2017

New J. Chem.

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Rhodium-catalysed hydroformylation is the major industrial process to obtain aldehyde products from olefins. The isomerization of the olefin at the catalyst is the most prominent side reaction and lowers the overall yield of the process. We here investigate whether the olefin isomer distribution obtained from batch experiments using Rh(BiPhePhos) as a catalyst and n-decene as the olefin reaches the thermodynamic equilibrium and computational quantum chemical approaches are able to accurately reproduce the experimental olefin isomer distribution. The relative energies of cis/trans configurational and double bond positional isomers of long chain n-decene were calculated using Hartree-Fock, DFT and correlated ab initio methods. Results were compared to experimental data. Electron correlation was found to be critical for the description of cis-isomer relative energies. Dispersion corrections in the DFT calculations partially compensate for deficiencies and generally improve the agreement with experiment. Adding thermodynamic corrections suffers from the neglect of certain contributions to the entropy of flexible molecules. Accounting for the entropy of mixing of multiple conformers significantly reduces the deviation from experiment. The equilibrium distribution of long chain olefins is reasonably described by correlated QM and also some density functional methods. Computational thermochemistry has thus reached a state where it provides reliable parameters for complex reaction network models and process engineering.

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Section: Discussionmentioning

confidence: 99%

The thermochemistry of long chain olefin isomers during hydroformylation

Kohls

Stein

2017

New J. Chem.

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“…Hydroformylation is a suitable way of converting these feedstocks into valuable intermediates like aldehydes. A carbon double bond can be converted into an aldehyde group with the addition of 2 and in hydroformylation using an homogeneous catalyst (Hentschel et al, 2015;Kaiser et al, 2016).…”

Section: Problem Formulationmentioning

confidence: 99%

“…The reaction network is illustrated in Fig. 2 (Hentschel et al, 2015). Equimolar content of CO and H 2 in the syngas is assumed.…”

Section: Problem Formulationmentioning

confidence: 99%

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NMPC using Pontryagin’s Minimum Principle-Application to a two-phase semi-batch hydroformylation reactor under uncertainty

Aydın

Bonvin

Sundmacher

2018

Computers & Chemical Engineering

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Nonlinear model predictive control (NMPC) is an important tool to perform real-time optimization for batch and semi-batch processes. Direct methods are often the methods of choice to solve the corresponding optimal control problems, in particular for large-scale problems. However, the matrix factorizations associated with large prediction horizons can be computationally demanding. In contrast, indirect methods can be competitive for smallerscale problems. Furthermore, the interplay between states and co-states in the context of Pontryagin's Minimum Principle might turn out to be computationally quite efficient. This work proposes to use an indirect solution technique within shrinking-horizon in the context of NMPC. In particular, the technique deals with path constraints via indirect adjoining, which allows meeting active path constraints explicitly at each iteration. Uncertainties are handled by the introduction of time-varying backoff terms for the path 2 constraints. The resulting NMPC algorithm is applied to a two-phase semi-batch reactor for the hydroformylation of 1-dodecene in the presence of uncertainty, and its performance is compared to that of NMPC that uses a direct simultaneous optimization method. The results show that the proposed algorithm (i) can enforce feasible operation for different uncertainty realizations both within batch or from batch to batch, and (ii) it is significantly faster than direct simultaneous NMPC, especially at the beginning of the batch. In addition, a modification of the PMP-based NMPC scheme is proposed that enforces active constraints via tracking.

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“…Besides the main reaction, isomerization to iso-dodecene, hydrogenation to n-dodecane and formation of the branched iso-aldehyde take place. Hernández and Engell [10] adapted the model developed by Hentschel et al [11] to the TMS miniplant by considering the material balances of the above components as follows:…”

Section: Simulation Studiesmentioning

confidence: 99%

A Study of Explorative Moves during Modifier Adaptation with Quadratic Approximation

2016

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Modifier adaptation with quadratic approximation (in short MAWQA) can adapt the operating condition of a process to its economic optimum by combining the use of a theoretical process model and of the collected data during process operation. The efficiency of the MAWQA algorithm can be attributed to a well-designed mechanism which ensures the improvement of the economic performance by taking necessary explorative moves. This paper gives a detailed study of the mechanism of performing explorative moves during modifier adaptation with quadratic approximation. The necessity of the explorative moves is theoretically analyzed. Simulation results for the optimization of a hydroformylation process are used to illustrate the efficiency of the MAWQA algorithm over the finite difference based modifier adaptation algorithm.

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Model-Based Identification and Experimental Validation of the Optimal Reaction Route for the Hydroformylation of 1-Dodecene

Cited by 51 publications

References 21 publications

The thermochemistry of long chain olefin isomers during hydroformylation

The thermochemistry of long chain olefin isomers during hydroformylation

NMPC using Pontryagin’s Minimum Principle-Application to a two-phase semi-batch hydroformylation reactor under uncertainty

A Study of Explorative Moves during Modifier Adaptation with Quadratic Approximation

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